Generation of Hydrocarbon Fuels Having a Reduced Environmental Impact

ABSTRACT

The Fischer-Tropsch (FT) process can be controlled to create water that has desirable characteristics for use in secondary processes such as fracking or irrigation.

RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.14/218,702, filed Mar. 18, 2014, now U.S. Pat. No. 9,365,765. Thisapplication claims the benefit of U.S. Provisional Patent ApplicationNo. 61/801,983, filed Mar. 15, 2013.

FIELD OF THE INVENTION

This invention relates to water created in the Fischer-Tropsch processand methods of reducing the environmental impact of hydraulic fracturing(“fracking”).

INTRODUCTION

Fracking requires very large amounts of water, typically about 4 milliongallons (15 million liters) of water are required for the development ofeach well. This very large volume of water at fracking sites can requireover a thousand truck trips and/or substantial water pipelines fromfresh water sources, which could include well water. This inventionprovides water that can be used for fracking or other valuable uses.

SUMMARY OF THE INVENTION

Rather than obtaining fresh water and transporting the fresh water to afracking site, the invention creates water near the fracking site. Theinvention creates water in the Fischer-Tropsch reaction, (2n+1)H₂+nCO→C_(n)H_((2n+2))+H₂O. The Fischer-Tropsch (“FT”) reaction cancreate very substantial amounts of water. For example, an FT processthat makes 5000 barrels per day of liquid hydrocarbons creates about250,000 gallons of water per day which can be stored in tanks near thefracking site. Thus, in a broad aspect, the invention provides method offracking, comprising: creating water in a Fischer-Tropsch process toform created water; storing the created water in a location close to afracking site; and injecting the created water in a well in a frackingprocess. Preferably, the FT process is conducted within one mile (1.6km) or less of a fracking site.

Fuel sources for the FT process can be found near potential frackingsites or from fracking sites themselves. A problem with the FT processis that it creates water with high chemical oxygen demand (COD) that mayneed treatment prior to release. However, according to the presentinvention, water created in the FT process can be used directly forfracking without first passing the water through a water treatmentfacility. The FT process may be part of an integrated synthetic fuelsfacility which could use local sources of carbonaceous materials toproduce synthesis gas. The carbonaceous materials may include naturalgas, including shale gas, coal bed methane, natural gas liquids, oil,coal, bitumen, biogas, landfill gas, refuse, and combinations thereof.The conversion of carbonaceous fuels to synthesis gas may include steamreforming, autothermal reforming, partial oxidation, gasification,including underground coal gasification, and combinations thereof. Theresulting synthesis gas is fed to a Fischer-Tropsch process, subsequentto any required gas clean-up processes required to meet synthesis gasfeed specifications to the Fischer-Tropsch process. The Fischer-Tropschprocess converts the synthesis gas to a mixture of water andhydrocarbons (primarily parrafinic, with some olefins and oxygenates).Fischer-Tropsch produced water is cleaner than many other sources ofwater from industrial facilities, since the FT reaction does not producearomatics, halides, heavy metals, or some of the other waste watercontaminants of concern.

In a first aspect, the invention provides a method of fracking,comprising: creating water in a Fischer-Tropsch (FT) process to formcreated water; storing the created water in a location close to afracking site; and injecting the created water in a well at the frackingsite. The meaning of “a location close to a fracking site” is theconventional understanding that the location is nearby so that the watercan be injected into a well; this is routinely done for frackingoperations. In some preferred embodiments, the FT process is conductedwithin 1.6 km of the fracking site.

In some preferred embodiments, a product stream from the FT process isseparated into a first aqueous stream and a second aqueous stream;wherein the first aqueous stream contains a lower concentration ofcarbon than the second aqueous stream; and wherein water from the firstaqueous stream is stored and injected into the well at the frackingsite. In some preferred embodiments, either all the water recovered froman FT process or at least a portion of the first aqueous stream or atleast a portion of the second aqueous stream is subjected to a strippingoperation where a gas is passed through the first aqueous stream. Insome embodiments, at least a portion of the second aqueous stream isreacted in a steam reforming reaction or an autothermal reformingreaction.

Preferably, the FT process is conducted in the presence of a FT catalystat a contact time of less than 1 second. Also, preferably, the FTprocess is conducted in a microchannel. In some preferred embodiments,the created water that is injected into the well has a concentration ofmethanol that is more than 10 times greater than any other alcohol. Inmany cases, a low pH is desirable for a fracking operation; however, insome embodiments, a base is added to the created water either forfracking or for other uses such as irrigation or as drinking water. Forfracking it is typically desirable to add particulates to the createdwater prior to injecting the created water in the well at the frackingsite.

The invention also provides a useful created water composition,comprising: at least 90% water; less than 20 mg/L, or 10 mg/L, of eachof the following: formaldehyde, propionaldehyde, butyraldehyde, diethylketone; at least 10 mg/L of each of the following: formic acid, aceticacid, propionic acid, n-butryic acid, and n-valeric acid; and at least50 mg/L methanol wherein the mass ratio of methanol to the sum of(propanol+butanol+pentanol+hexanol+heptanol+octanol+nonanol) is greaterthan 1, or greater than 2 or greater than 5 or greater than 10 orgreater than 50. In some preferred embodiments, the water compositionmay possess one or any combination of the following characteristics: 10ppm or less aromatics; pH between 3.0 and 3.5; 40 mg/L, 20 mg/L, 10mg/L, 5 mg/L or less acetone; 50 to 8000 mg/L methanol or 50 to 4000mg/L methanol; up to about 3500, or up to about 1000, or up to about 500mg/L ethanol; a mass ratio of formic acid to methanol at least 0.030, orat least 0.08; a mass ratio of propionic acid to propanol at least0.030, or at least 0.06, or at least 1.0; a ¹⁴C/¹³C ratio is at least90% lower than present in biological carbon (this identifies the carbonas a fossil fuel source); 0.1 to 1.0% C; less than 1.0 mg/L of each ofthe following: formaldehyde, propionaldehyde, butyraldehyde, diethylketone; less than 0.1 mg/L of each of the following: formaldehyde,propionaldehyde, butyraldehyde, and diethyl ketone. The water is usefulfor fracking, irrigation, and with additional treatment, drinking water.

The invention also includes methods of treating water created in the FTprocess. Thus, in one aspect, the invention provides a method oftreating water created in a FT process, comprising: conducting an FTprocess to form a product stream; separating the product stream into anaqueous stream and a hydrocarbon product stream; subjecting the aqueousstream to a stripping operation where a gas is passed through theaqueous stream and thereby producing a stripped aqueous stream; andusing the stripped aqueous stream in a secondary process comprisingfracking or irrigation. In one embodiment, the product stream isseparated into a first aqueous stream and a second aqueous stream;wherein the first aqueous stream contains a lower concentration ofcarbon than the second aqueous stream; subjecting at least a portion ofthe first aqueous stream to a stripping operation where a gas is passedthrough the first aqueous stream and thereby producing a first strippedstream; using the stripped stream in a secondary process; and passingthe second aqueous stream to a waste treatment facility. In analternative embodiment, the second aqueous stream is subjected to astripping operation where a gas is passed through the second aqueousstream and thereby producing a second stripped stream.

In describing the stripping step(s), the term “gas” does not distinguishbetween gases and vapors; thus steam is included in the classificationof a “gas”. In some preferred embodiments, the stripping gas comprisessteam, air, N2, tail gas, natural gas, and combinations thereof. Any ofthe aqueous streams may be further treated in a waste treatmentfacility, preferably using a biological treatment to removecontaminants.

In some preferred embodiments, a product stream from an FT process ispassed through a first condenser forming a first aqueous stream, a firsthydrocarbon stream, and a vapor stream. This vapor stream can then bepassed into a second condenser to recover a second aqueous stream. Thefirst aqueous stream has a significantly lower carbon content and may bemore suitable for fracking than the second aqueous stream. The firstaqueous stream may also be recycled for use in the step to convert thecarbonaceous materials to synthesis gas. A portion of this first aqueousstream that is not used for fracking and/or recycle to the process maybe sent to a water treatment system. Preferably, the first aqueousstream comprises 0.01 to 1% carbon, in some embodiments 0.1 to 0.7%, insome embodiments 0.2 to 0.5% carbon (% is mass % unless indicatedotherwise). In some preferred embodiments, the second aqueous streamcomprises 0.5 to 10% carbon, in some embodiments 1 to 5%, in someembodiments 2 to 4%. In some embodiments, the first aqueous streamcomprises 50 to 95% of the water produced in the FT process, in someembodiments at least 60%, in some embodiments at least 70%, and in someembodiments at least 80%. The second aqueous stream comprises 5 to 30%of the water produced in the FT process, in some embodiments 20% orless, in some embodiments 15% or less of the water produced in the FTprocess. In some preferred embodiments, at least 50%, at least 60%, atleast 70%, or at least 80% and up to 95% or up to 90% of the waterrecovered from the FT process is injected in a well (or wells) in afracking operation (or operations).

The first aqueous stream (or alternatively stated, a relatively higherboiling (or more easily condensable) fraction which may comprise 50 to95% of the water produced in the FT process, in some embodiments atleast 60%, in some embodiments at least 70%, and in some embodiments atleast 80% of the water produced in the FT process) comprises alcoholsthat can improve the fracking process and relatively little hydrocarbons(non-alcohols). The carbon compounds in the second aqueous stream (oralternatively stated, a relatively lower boiling (or less easilycondensable) fraction have a lower mass ratio of alcohol tohydrocarbons. In some preferred embodiments, the first aqueous stream isstored for fracking and the second aqueous stream is sent to a watertreatment facility.

Any of the method steps discussed in this specification can beincorporated into the method of fracking discussed above.

Stripping

In some preferred aspects of the invention, some or all of the watercreated in the FT process is subjected to a stripping operation. In somepreferred aspects, the stripper pressure is slightly above atmosphericpressure and the temperature of the mixture at any point in the columnwill be at the mixture bubble point. In some preferred aspects, thestripping can be done by flowing the FT water down a column with packingor trays, with the stripping fluid (e.g. steam) in counter-currentcontact. The stripping may be done under vacuum or slightly aboveatmospheric pressure (for example, 0.1-10 atm). The temperature will bebelow the boiling temperature of the FT water. The mass ratio ofstripping medium to FT water may be 0.001 to 0.5, more preferably 0.01to 0.2.

Water created in an FT process conducted at contact times of 1 second orless and/or short diffusion distances (e.g. FT catalyst thickness of 100μm or less) and/or an FT process conducted under the conditionsdescribed below) is superior to water created by conventional FT or manyother industrial waste water compositions. Advantages of the createdwater obtained as described herein may include one or more of thefollowing features: very low concentration of aromatics (e.g., 10 ppm orless); low aldehyde concentration, and wherein the carbon present in thewater is nearly exclusively (e.g., at least 90% by mass, or at least 95%by mass, or at least 98% by mass, or lat least 99% by mass) in the formof biodegradable acids (i.e., formic, acetic, propionic, n-butyric,n-valeric, and caproic), methanol, or ethanol.

The invention also includes a storage tank or basin near a fracking sitethat comprises the water composition described here. Likewise, theinvention includes a method of using the water composition in frackingor irrigation.

Shown below is a table listing the composition of water created by a FTprocess as described herein and results from a modeling simulation afterstripping with steam at 5, 10, or 15% of the feed water mass flow.

Data Source Bench-scale sample Pilot-scale sample Stripped waterStripped Water 5% 10% 15% 5% 10% 15% General Feed steam steam steam Feedsteam steam steam pH 3.18 3.29 Ketones Acetone mg/l 35.9 14.2 0.0 0.052.3 17.5 0.0 0.0 Diethyl mg/l 0.161 0.0 0.0 0.0 0.181 0.0 0.0 0.0Ketone Aldehydes Formaldehyde mg/l 0.13 0.0 0.0 0.0 Not 0.0 0.0 0.0detected Acetaldehyde mg/l 26.1 0.0 0.0 0.0 <10 0.0 0.0 0.0Propionaldehyde mg/l <10 0.0 0.0 0.0 <10 0.0 0.0 0.0 Butyraldehyde mg/l<10 0.0 0.0 0.0 <10 0.0 0.0 0.0 Acids Formic Acid mg/l 127 125.0 123.7122.2 108 105.8 104.8 103.6 Acetic Acid mg/l 270 259.5 256.6 252.9 261250.0 247.3 244.1 Propionic Acid mg/l 26.6 28.7 27.8 26.8 20.4 19.1 18.617.9 n-Butyric Acid mg/l 21.7 19.0 17.9 16.6 22.8 19.0 17.9 16.7n-Valeric Acid mg/l 19.9 19.0 17.9 16.6 23.8 19.0 18.0 16.8 Caproic Acidmg/l 11.9 9.5 9.0 8.5 19.4 19.1 18.1 17.1 Alcohols Methanol mg/l 39003349.3 1583.5 98.5 7780 6661.6 3232.0 227.5 Ethanol mg/l 3310 2673.0449.8 0.7 2450 1969.5 371.2 0.6 Propanol mg/l 980 460.8 0.0 0.0 690329.5 0.0 0.0 Butanol mg/l 622 459.7 6.2 0.0 446 318.0 0.0 0.0 Pentanolmg/l 307 230.0 2.7 0.0 251 184.8 0.0 0.0 Hexanol mg/l 102 67.7 0.1 0.094.2 61.2 0.0 0.0 Heptanol mg/l 26.3 20.0 0.0 0.0 28 20.2 0.0 0.0Octanol mg/l 8.9 0.0 0.0 0.0 10.2 0.0 0.0 0.0 Nonanol mg/l 5 6.7 0.0 0.05.2 6.8 0.0 0.0 Decanol mg/l 5.6 6.6 0.0 0.0 5.4 6.7 0.0 0.0

FT processes that are conducted in microchannels comprising an FTcatalyst and/or at short contact times with an FT catalyst areespecially desirable since such processes result in a superior mix ofcomponents as compared to conventional FT processes. For purposes of thepresent invention, a microchannel is defined as a channel having atleast one internal dimension of 10 mm or less; in some preferredembodiments 5 mm or less. In preferred embodiments, the FT reaction isconducted through a planar array of microchannels that are adjacent to aplanar array of coolant channels. Short contact times are preferablyless than 1 second, more preferably less than 500 msec, and in someembodiments in the range of 150 to 500 ms.

Water created by the preferred FT methods mentioned in this disclosureare believed to be superior because the process makes lower amounts ofalcohols in total (relative to conventional FT processes), and morespecifically the low amounts in the larger hot separator water stream(normally in the range of 0.2-0.5%). Alcohols are a common additive towater employed for fracking but the amounts are generally low.

In some preferred embodiments, a fracking process is conducted usingwater created from an FT process conducted in microchannels comprisingan FT catalyst and/or at short contact times with an FT catalyst, or,optionally using any one or any combination of the FT process conditionsand/or system characteristics, such as catalyst size and/or composition,optionally in combination with other selected process conditions. Insome preferred embodiments, the invention comprises conducting frackingusing created water having a carbon content of 1% or less, in someembodiments 0.7% or less, and in some embodiments 0.5% or less, in someembodiments in the range of 0.1 to 1%, in some embodiments 0.3% or less.

The lower levels of alcohols generated in the FT processes mentionedherein are believed to occur, especially when the process is run at veryhigh reaction rates (short contact times) and, preferably, withmoderately sized catalyst particles, and as a result, operate with asignificant amount of mass transfer limitations—specifically catalystpore diffusion limitations.

The mass transfer coefficient for CO is a lot smaller than the one forH₂, so when mass transfer limitations become significant CO is affectedprimarily. The local H₂/CO (inside catalyst pellets) increases, even asthe concentrations of both decrease. Increasing H₂/CO ratio increasesthe extent of hydrogenation of the products, meaning less olefins andalcohols and more paraffins.

It can also be noted that FT water is also acidic (both the first andsecond separated streams) and tends to have a pH in the range of3.0-3.5. Mineral acids are a common ingredient of fracking fluids.

Prior to use in fracking, the created water may be modified by addingone or more of the following: a particulate (such as sand or otherparticulates), a thickener (such as guar gum or a polysaccharide), aclay stabilizer (such as sodium chloride or an ammonium salt), and ascale inhibitor (such as a phosphonic acid).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view of an FT test reactor.

GLOSSARY

The term “microchannel” may refer to a channel having at least oneinternal dimension of height or width of up to about 10 millimeters(mm), and in one embodiment up to about 5 mm, and in one embodiment upto about 2 mm, and in one embodiment up to about 1 mm. The microchannelmay comprise at least one inlet and at least one outlet wherein the atleast one inlet is distinct from the at least one outlet. Themicrochannel may not be merely an orifice. The microchannel may not bemerely a channel through a zeolite or a mesoporous material. The lengthof the microchannel may be at least about two times the height or width,and in one embodiment at least about five times the height or width, andin one embodiment at least about ten times the height or width. Theinternal height or width of the microchannel may be in the range ofabout 0.05 to about 10 mm, and in one embodiment from about 0.05 toabout 5 mm, and in one embodiment from about 0.05 to about 2 mm, and inone embodiment from about 0.05 to about 1.5 mm, and in one embodimentfrom about 0.05 to about 1 mm, and in one embodiment from about 0.05 toabout 0.75 mm, and in one embodiment from about 0.05 to about 0.5 mm.The other internal dimension of height or width may be of any dimension,for example, up to about 3 meters, and in one embodiment about 0.01 toabout 3 meters, and in one embodiment about 0.1 to about 3 meters. Thelength of the microchannel may be of any dimension, for example, up toabout 10 meters, and in one embodiment from about 0.1 to about 10meters, and in one embodiment from about 0.2 to about 10 meters, and inone embodiment from about 0.2 to about 6 meters, and in one embodimentfrom 0.2 to about 3 meters. The microchannel may have a cross sectionhaving any shape, for example, a square, rectangle, circle, semi-circle,trapezoid, etc. The shape and/or size of the cross section of themicrochannel may vary over its length. For example, the height or widthmay taper from a relatively large dimension to a relatively smalldimension, or vice versa, over the length of the microchannel.

The term “microchannel reactor” may refer to an apparatus comprising oneor more process microchannels wherein an FT process is conducted. Whentwo or more process microchannels are used, the process microchannelsmay be operated in parallel. The microchannel reactor may include aheader or manifold assembly for providing for the flow of fluid into theone or more process microchannels, and a footer or manifold assemblyproviding for the flow of fluid out of the one or more processmicrochannels. The microchannel reactor may comprise one or more heatexchange channels adjacent to and/or in thermal contact with the one ormore process microchannels. The heat exchange channels provide heatingand/or cooling for the fluids in the process microchannels. Themicrochannel reactor may include a header or manifold assembly forproviding for the flow of heat exchange fluid into the heat exchangechannels, and a footer or manifold assembly providing for the flow ofheat exchange fluid out of the heat exchange channels.

The term “process microchannel” may refer to a microchannel wherein anFT process is conducted.

The term “contact time” refers to the volume of a reaction zone within amicrochannel divided by the volumetric feed flow rate of the reactantsat a temperature of 0° C. and a pressure of one atmosphere.

The term “fresh synthesis gas” refers to synthesis gas that flows into amicrochannel reactor and is used as a reactant in a Fischer-Tropschreaction. The fresh synthesis gas does not contain any recycledcomponents from the product produced during the Fischer-Tropschreaction. The term “fresh synthesis gas” refers to a gaseous mixturethat contains CO and H₂ and is not part of the recycled tail gas that isused during the inventive process. Synthesis gas may be referred to assyngas. The fresh synthesis gas can be combined with recycled tail gas,which also contains H₂ and CO, to form the reactant mixture used withthe FT process. The reactant mixture may comprise H₂ and CO with a molarratio of H₂ to CO that may be in the range from about 1.4:1 to about2.1:1, or from about 1.5:1 to about 2:1:1, or from about 1.6:1 to about2:1, or from about 1.7:1 to about 1.9:1. The fresh synthesis gas maycomprise H₂ and CO with the molar ratio of H₂ to CO being in the rangefrom about 1.9:1 to about 2.1:1, or from about 1.95:1 to about 2.05:1,or from about 1.98:1 to about 2.02:1. The tail gas that is generatedduring the FT process and combined with the fresh synthesis gas to formthe reactant mixture may be referred to as recycled tail gas. Therecycled tail gas may comprise H₂ and CO with a molar ratio of H₂ to COin the range from about 0.5:1 to about 2:1, or from about 0.6:1 to about1.8:1, or from about 0.7:1 to about 1.2:1. The volumetric ratio of thefresh synthesis gas to the tail gas in the reactant mixture may be inthe range from about 1:1 to about 10:1, or from about 1:1 to about 8:1,or from about 1:1 to about 6:1, or from about 1:1 to about 4:1, or fromabout 3:2 to about 7:3, or about 2:1.

The term “tail gas” refers to a gaseous product produced during aFisher-Tropsch reaction. The tail gas may contain CO and H₂.

The term “reactant mixture” refers to a mixture of fresh synthesis gas,and a tail gas or tail gas components (e.g., CO and H₂) recycled fromthe Fischer-Tropsch reaction.

The term “conversion of CO” refers to the CO mole change between thefresh synthesis gas in the reactant mixture and product, divided by themoles of CO in the fresh synthesis gas.

The term “one-pass conversion of CO” refers to the conversion of CO fromthe overall reactant mixtures (i.e., fresh synthesis gas plus recycledtail gas or recycled tail gas components) after one pass through themicrochannel reactor.

The term “selectivity to methane” refers to the moles of methane in theproduct minus the moles of methane in the reactant mixture, divided bymoles of the CO that are consumed in the reaction.

The term “Fischer-Tropsch product” or “FT product” refers to ahydrocarbon product made by a Fischer-Tropsch process. The FT liquidproduct may have a boiling point at or above about 30° C. at atmosphericpressure.

The term “FT tail gas” or “tail gas” refers to a gaseous product made bya Fischer-Tropsch process. The tail gas may have a boiling point belowabout 30° C. at atmospheric pressure. The tail gas may contain H₂ andCO.

The term “Co loading” may refer to the weight of Co in a catalystdivided by the total weight of the catalyst, that is, the total weightof the Co plus any co-catalyst or promoter as well as any support. Ifthe catalyst is supported on an engineered support structure such as afoam, felt, wad or fin, the weight of such engineered support structuremay not be included in the calculation. Similarly, if the catalyst isadhered to a channel wall, the weight of the channel wall may is not beincluded in the calculation.

The Fischer-Tröpsch Process

Examples of Fischer-Tröpsch processes suitable for use in the presentinvention are described in US Published Patent Application No.20100081726 and WO2012107718 which are incorporated herein by reference.The following are some non-limiting descriptions of some preferredembodiments of the FT process that can be used for creating water inconjunction with the present invention:

Suitable apparatus for conducting the FT process is known in the priorart. Preferred apparatus are microchannel reactors. A microchannelreactor may be made of any material that provides sufficient strength,dimensional stability and heat transfer characteristics to permitoperation of the desired process. These materials may include aluminum;titanium; nickel; platinum; rhodium; copper; chromium; alloys of any ofthe foregoing metals; brass; steel (e.g., stainless steel); quartz;silicon; or a combination of two or more thereof. Each microchannelreactor may be constructed of stainless steel with one or more copper oraluminum waveforms being used for forming the channels. In preferredembodiments, the FT reactor is not a fluidized bed reactor.

The microchannel reactor may comprise a plurality of plates or shims ina stack defining a plurality of Fischer-Tropsch process layers and aplurality of heat exchange layers, each plate or shim having aperipheral edge, the peripheral edge of each plate or shim being weldedto the peripheral edge of the next adjacent plate or shim to provide aperimeter seal for the stack. This is shown in U.S. Published PatentApplication No. 2012/0095268, which is incorporated herein by reference.

The microchannel reactor may be constructed using waveforms in the formof corrugated inserts. These corrugated sheets may have corrugationswith right-angles and may have rounded edges rather than sharp edges.These inserts may be sandwiched between opposing planar sheets or shims.In this manner the microchannels may be defined on three sides by thecorrugated insert and on the fourth side by one of the planar sheets.The process microchannels as well as the heat exchange channels may beformed in this manner. Microchannel reactors made using waveforms aredisclosed in U.S. Pat. No. 8,720,725, which is incorporated herein byreference.

The FT microchannel reactor may comprise at least one processmicrochannel in thermal contact with a heat exchanger, the catalystbeing in the process microchannel. The microchannel reactor may comprisea plurality of process microchannels and a plurality of heat exchangechannels, the catalyst being in the process microchannels.

The microchannel reactor may comprise a plurality of processmicrochannels and a plurality of heat exchange channels, the catalystbeing in the process microchannels, each heat exchange channel being inthermal contact with at least one process microchannel, at least onemanifold for flowing the reactant mixture into the processmicrochannels, at least one manifold for flowing product out of theprocess microchannels, at least one manifold for flowing a heat exchangefluid into the heat exchange channels, and at least one manifold forflowing the heat exchange fluid out of the heat exchange channels.

A plurality of the microchannel reactors may be positioned in a vessel,each microchannel reactor comprising a plurality of processmicrochannels and a plurality of heat exchange channels, the catalystbeing in the process microchannels, each heat exchange channel being inthermal contact with at least one process microchannel, the vessel beingequipped with a manifold for flowing the reactant mixture to the processmicrochannels, a manifold for flowing the product from the processmicrochannels, a manifold for flowing a heat exchange fluid to the heatexchange channels, and a manifold for flowing the heat exchange fluidfrom the heat exchange channels. The process microchannel having fluidflowing in it in one direction, the heat exchange channel having fluidflow in a direction that is co-current, counter-current or cross-currentto the flow of fluid in the process microchannel.

The microchannel reactor may comprise at least one process microchanneland at least one heat exchanger, a tailored heat exchange profile beingprovided along the length of the process microchannel, the local releaseof heat given off by the reaction conducted in the process microchannelbeing matched with cooling provided by the heat exchanger.

The microchannel reactor may comprise a plurality of processmicrochannels, the process microchannels being formed by positioning awaveform between planar sheets. The microchannel reactor may furthercomprises a plurality of heat exchange channels in thermal contact withthe process microchannels, the heat exchange channels being formed bypositioning a waveform between planar sheets.

The catalyst may be in the form of particulate solids. The microchannelreactor comprises one or more process microchannels, and the catalystmay be coated on interior walls of the process microchannels or grown oninterior walls of the process microchannels. The catalyst may besupported on a support having a flow-by configuration, a flow-throughconfiguration, or a serpentine configuration. The catalyst may besupported on a support having the configuration of a foam, felt, wad,fin, or a combination of two or more thereof.

In preferred aspects, the catalyst can be disposed on a support thatcomprises a refractory metal oxide, carbide, carbon, nitride, or mixtureof two or more of these. The support may comprise alumina, zirconia,silica, titania, or a mixture of two or more of these. The support maycomprise a TiO₂ modified silica support wherein the support contains atleast about 5% by weight TiO₂, or from about 5% to about 30% by weightTiO₂, or from about 1 to about 17% by weight TiO₂, or about 16% byweight TiO₂. The surface of the surface modified support may beamorphous. A catalyst precursor may comprise a cobalt oxide, such asCo₃O₄.

The preferred FT catalyst comprises Co and preferably comprises at leastone secondary catalyst metal. Suitable secondary catalyst metals mayinclude noble metals, such as Pd, Pt, Rh, Ru, Jr, Au, Ag and Os,transition metals, such as Zr, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb,Mo, Tc, Cd, Hf, Ta, W, Re, Hg and Ti and the 4f-block lanthanides, suchas La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and/or Lu.

The secondary catalyst metal may be one or more of Pd, Pt, Ru, Ni, Co(if not the primary catalyst metal), Fe (if not the primary catalystmetal), Cu, Mn, Mo, Re and W.

The catalyst may be dispersed on a surface modified support to anchorthe catalyst particles and provide mechanical strength. The support maycomprise a refractory metal oxide, carbide, carbon, nitride, or mixtureof two or more thereof. The support may comprise alumina, zirconia,silica, titania, or a mixture of two or more thereof. The surface of thesupport may be modified by treating it with titania, zirconia, magnesia,chromia, silica, alumina, or a mixture of two or more thereof. Thematerial used for the support and the material used for modifying thesupport may be different. While not wishing to be bound by theory, it isbelieved that the surface treatment provided for herein helps keep theCo from sintering during operation of the inventive Fischer-Tropschprocess.

The support may comprise silica and the surface of the silica may becoated with an oxide refractory solid oxide, in particular titania. Thecatalyst support may be in the form of a structured shape, pellets or apowder.

The support may comprise a titania modified silica support. Titania(TiO₂) may be used to increase the stability (e.g. by decreasingdeactivation) of the silica-supported catalyst.

At elevated temperatures, the catalyst material may react with thesurface Si—OH groups on a silica support to generate silicate specieswhich are not Fischer-Tropsch active and may not be readily reducible.This may lead to a loss in active surface area of the catalyst andtherefore a drop in Fischer-Tropsch synthesis activity.

Without wishing to be bound by theory, it is believed that dispersion oftitania onto a silica surface occurs via consumption of the surfaceSi—OH groups with the subsequent forming of bridging Ti—O—Si bonds.Thus, modification of a silica support with a layer of titania mayremove the Si—OH groups and thereby prevent the formation of silicates.

TiO₂ may comprise at least 11 wt %, or greater than 11 wt %, of thetotal weight of the catalyst support. In particular, the catalystsupport may comprise 11-30 wt %, 11-25 wt %, 11-20 wt %, or 12-18 wt %,or 15-17 wt %, or about 16 wt % TiO₂ on silica (SiO₂).

In one embodiment, the catalyst precursor may comprise from about 40 toabout 44 wt % Co, from about 0.1 to about 0.3 wt % Re, and from about0.01 to about 0.05 wt % Pt (each expressed as a percentage of the totalweight of the catalyst precursor); and a TiO₂-modified silica catalystsupport, comprising from about 11 to about 30 wt % TiO₂ (expressed as apercentage of the total weight of the catalyst support).

The activity and the selectivity of cobalt-based catalysts may beinfluenced by the density of active sites, favouring very small particlesizes. However, the deactivation mechanisms of cobalt catalysts mayfollow in general the reverse trend, where the largest particles may bethe most stable.

The numerical average particle diameter of Co₃O₄ may be less than about12 nm (determined by powder X-ray diffraction, for example, using aSiemens D5000 theta/theta powder diffractometer and CuK, radiation). Thecobalt oxide particle size distribution may influence catalyst activityand stability, such that, a particle size distribution as narrow aspossible may be useful. The width of the particle size distribution canbe measured by the c value of the lognormal particle size distribution.c is a dimensionless ratio, and characterizes the width of the sizedistribution. The c value of the lognormal particle size distribution ofCo₃O₄ particles may be less than about 0.31. The average particlediameter of Co₃O₄ may be below about 11 nm, or between about 8 and about10 nm. The c value may be between about 0.19 and about 0.31, or belowabout 0.25, or between about 0.19 and about 0.25. Where the numericalaverage particle diameter of the Co₃O₄ is in the range of about 8 toabout 10 nm, c may be less than 0.31.

The characteristics of the Co₃O₄ particles may be affected by thesynthetic procedure by which the catalyst precursor and catalyst areproduced.

In particular, where the catalyst comprises a TiO₂-modified silicasupport, the use of a titanium alkoxide (e.g. titanium isopropoxide) tomodify the support can provide a catalyst comprising Co₃O₄ having theabove properties. In this embodiment, the catalyst precursor may containless than 10%, or less than 5%, or preferably less than 1% crystallineTiO₂ (expressed as a percentage of all of the TiO₂ in the catalystprecursor). Alternatively, all of the TiO₂ present in the catalystprecursor may be amorphous or not crystalline (up to detectable limits).

Alternatively, where the catalyst comprises a TiO₂-modified silicasupport, an aqueous method (e.g. using titanium (IV)bis(ammoniumlactato)dihydroxide) may be used to modify the support inplace of using a titanium alkoxide. A preferred aqueous method is asdescribed in the section headed “Aqueous Treating of Catalyst Support”below. The resulting modified support is also able to provide a catalystcomprising Co₃O₄ having the above properties.

Similarly, the use of citric acid as fuel/reducing agent in theproduction of the catalyst precursor can provide a catalyst precursorand a catalyst comprising Co₃O₄ having the above properties.

Also, the number of impregnations used to form a catalyst may affect theparticle size distribution.

The catalyst may be supported on a flow-through support structure suchas a foam, wad, pellet, powder, or gauze. The flow-through catalyst iscontained within a process microchannel, the reactants flowing throughthe catalyst.

The support structure for a flow-through catalyst may be formed from amaterial comprising silica gel, foamed copper, sintered stainless steelfiber, steel wool, alumina, or a combination of two or more thereof. Thesupport structure may be made of a heat conducting material, such as ametal, to enhance the transfer of heat to or from the catalyst.

The catalyst may be supported on a fin assembly comprising one or morefins positioned within the process microchannels. The fins project fromthe fin support into the interior of the process microchannel. The finsmay extend to and contact the interior surface of upper wall of processmicrochannel. Fin channels between the fins provide passageways forreactant and product to flow through the process microchannel parallelto its length. Each of the fins has an exterior surface on each of itssides. The exterior surface provides a support base for the catalyst.The reactants may flow through the fin channels, contact the catalystsupported on the exterior surface of the fins, and react to formproduct. Each of the fins may have a height ranging from about 0.02 mmup to the height of the process microchannel, or from about 0.02 toabout 10 mm, or from about 0.02 to about 5 mm, or from about 0.02 toabout 2 mm. The width of each fin may range from about 0.02 to about 5mm, or from about 0.02 to about 2 mm, or about 0.02 to about 1 mm. Thelength of each fin may be of any length up to the length of the processmicrochannel, or up to about 10 m, or about 0.5 to about 10 m, or about0.5 to about 6 m, or about 0.5 to about 3 m. The gap between each of thefins may be of any value and may range from about 0.02 to about 5 mm, orfrom about 0.02 to about 2 mm, or from about 0.02 to about 1 mm. Thenumber of fins in the process microchannel may range from about 1 toabout 50 fins per centimeter of width of the process microchannel, orfrom about 1 to about 30 fins per centimeter, or from about 1 to about10 fins per centimeter, or from about 1 to about 5 fins per centimeter,or from about 1 to about 3 fins per centimeter. Each of the fins mayhave a cross-section in the form of a rectangle or square. When viewedalong its length, each fin may be straight, tapered or have a serpentineconfiguration. The fin assembly may be made of any material thatprovides sufficient strength, dimensional stability and heat transfercharacteristics to permit operation for which the process microchannelis intended. These materials include: steel (e.g., stainless steel,carbon steel, and the like); aluminum; titanium; nickel; platinum;rhodium; copper; chromium; alloys of any of the foregoing metals; monel;inconel; brass; polymers (e.g., thermoset resins); ceramics; glass;quartz; silicon; or a combination of two or more thereof. The finassembly may be made of an Al₂O₃ or a Cr₂O₃ forming material wherein alayer of Al₂O₃ or a Cr₂O₃ forms on the surface of the fin assembly whenthe fin assembly is heat treated in air. The fin assembly may be made ofan alloy comprising Fe, Cr, Al and Y, or an alloy comprising Ni, Cr andFe.

The catalyst may be supported on one or more corrugated insertspositioned in slots within the microchannel reactor. The slots maycomprise microchannels, and have the dimensions indicated above as beingmicrochannels. Alternatively, the slots may have dimensions that wouldmake them larger than microchannels. The process microchannels of themicrochannel reactor may comprise the slots, or may be positioned withinthe corrugated inserts and/or formed by openings between the interiorsidewalls of the slots and the inserts. Each of the corrugated insertsmay have a height ranging from about 0.02 mm up to the height of theslot, or from about 0.02 to about 10 mm, or from about 0.02 to about 5mm, or from about 0.02 to about 2 mm. Each of the corrugated inserts mayhave a width ranging from about 0.02 mm up to the width of the slot, orfrom about 0.02 to about 10 mm, or from about 0.02 to about 5 mm, orfrom about 0.02 to about 2 mm. The length of each corrugated insert maybe of any length up to the length of the slot, or up to about 10 m, orabout 0.5 to about 10 m, or about 0.5 to about 6 m, or about 0.5 toabout 3 m. The corrugated inserts may be made of any material thatprovides sufficient strength, dimensional stability and heat transfercharacteristics to permit operation for which the microchannel reactoris intended. These materials include: steel (e.g., stainless steel,carbon steel, and the like); aluminum; titanium; nickel; platinum;rhodium; copper; chromium; alloys of any of the foregoing metals; monel;inconel; brass; polymers (e.g., thermoset resins); ceramics; glass;quartz; silicon; or a combination of two or more thereof. The corrugatedinserts may be made of an alloy that forms a layer of Al₂O₃ or Cr₂O₃ onthe surface of the inserts when heat treated in air. The corrugatedinserts may be made of an alloy comprising Fe, Cr, Al and Y, or an alloycomprising Ni, Cr and Fe.

The catalyst may be directly washcoated or grown from solution on theinterior walls of the process microchannels and/or on one or more of theabove-described catalyst support structures. The catalyst may be in theform of a single piece of porous contiguous material, or many pieces inphysical contact. The catalyst may comprise a contiguous material andhave a contiguous porosity such that molecules can diffuse through thecatalyst. In this embodiment, the fluids may flow through the catalystrather than around it. The cross-sectional area of the catalyst mayoccupy from about 1 to about 99%, or about 10 to about 95% of thecross-sectional area of the process microchannels.

In some preferred embodiments, the FT reaction may be conducted usingone or any combination of the following conditions:

The contact time of the reactants with the Fischer-Tropsch catalyst mayrange up to about 2000 milliseconds (ms), or in the range from about 10to about 2000 ms, or from about 10 ms to about 1000 ms, or about 20 msto about 500 ms, or from about 200 to about 400 ms, or from about 240 toabout 350 ms.

The space velocity (or gas hourly space velocity (GHSV)) for the flow offluid in the Fischer-Tropsch microchannels may be at least about 1000hr⁻¹ (normal liters of feed/hour/liter of volume within the processmicrochannels), or from about 1000 to about 1,000,000 hr⁻¹, or fromabout 5000 to about 20,000 hr⁻¹.

The pressure within the Fischer-Tropsch process microchannels may be upto about 100 atmospheres, or in the range from about 1 to about 100atmospheres, or from about 1 to about 75 atmospheres, or from about 2 toabout 40 atmospheres, or from about 2 to about 10 atmospheres, or fromabout 10 to about 50 atmospheres, or from about 20 to about 30atmospheres.

The pressure drop of fluids as they flow in the Fischer-Tropsch processmicrochannels may range up to about 30 atmospheres per meter of lengthof channel (atm/m), or up to about 25 atm/m, or up to about 20 atm/m.The pressure drop may be in the range from about 10 to about 20 atm/m.

The Reynolds Number for the flow of fluid in the Fischer-Tropsch processmicrochannels may be in the range of about 10 to about 4000, or about100 to about 2000.

The average temperature in the Fischer-Tropsch process microchannels maybe in the range from about 150 to about 300° C., or in the range fromabout 175 to about 240° C., of in the range from about 190 to about 230°C., or from about 195 to about 225° C.

The heat exchange fluid entering the heat exchange channels of themicrochannel reactor may be at a temperature in the range of about 100°C. to about 400° C., or about 200° C. to about 300° C. The heat exchangefluid exiting the heat exchange channels may be at a temperature in therange of about 150° C. to about 450° C., or about 200° C. to about 350°C. The residence time of the heat exchange fluid in the heat exchangechannels may range from about 1 to about 2000 ms, or about 10 to about500 ms. The pressure drop for the heat exchange fluid as it flowsthrough the heat exchange channels may range up to about 10 atm/m, orfrom about 1 to about 10 atm/m, or from about 3 to about 7 atm/m, orabout 5 atm/m. The heat exchange fluid may be in the form of a vapor, aliquid, or a mixture of vapor and liquid. The Reynolds Number for theflow of the heat exchange fluid in heat exchange channels may be fromabout 10 to about 4000, or about 100 to about 2000.

The heat exchange fluid used in the heat exchange channels in themicrochannel reactor may be any heat exchange fluid suitable for coolinga Fischer-Tropsch exothermic reaction. These may include air, steam,liquid water, gaseous nitrogen, other gases including inert gases,carbon monoxide, oils such as mineral oil, and heat exchange fluids suchas Dowtherm A and Therminol which are available from Dow-Union Carbide.

The heat exchange channels used in the microchannel reactor may compriseprocess channels wherein an endothermic process is conducted. These heatexchange process channels may be microchannels. Examples of endothermicprocesses that may be conducted in the heat exchange channels includesteam reforming and dehydrogenation reactions. Steam reforming of analcohol that occurs at a temperature in the range from about 200° C. toabout 300° C. is an example of an endothermic process that may be used.The incorporation of a simultaneous endothermic reaction to provide animproved cooling may enable a typical heat flux of roughly an order ofmagnitude above convective cooling.

The heat exchange fluid may undergo a partial or full phase change as itflows in the heat exchange channels of the microchannel reactor. Thisphase change may provide additional heat removal from the processmicrochannels beyond that provided by convective cooling. For a liquidheat exchange fluid being vaporized, the additional heat beingtransferred from the Fischer-Tropsch process microchannels may resultfrom the latent heat of vaporization required by the heat exchangefluid. In one embodiment, about 50% by weight of the heat exchange fluidmay be vaporized, or about 35% by weight may be vaporized, or about 20%by weight may be vaporized, or about 10% by weight, or about 5% byweight may be vaporized, or about 2 to about 3% by weight may bevaporized.

The heat flux for heat exchange in the microchannel reactor may be inthe range from about 0.01 to about 500 watts per square centimeter ofsurface area of the one or more heat transfer walls of the processmicrochannels (W/cm²) in the microchannel reactor, or in the range fromabout 0.1 to about 250 W/cm², or from about 1 to about 125 W/cm², orfrom about 1 to about 100 W/cm², or from about 1 to about 50 W/cm², orfrom about 1 to about 25 W/cm², or from about 1 to about 10 W/cm². Therange may be from about 0.2 to about 5 W/cm², or about 0.5 to about 3W/cm², or from about 1 to aobut 2 W/cm².

The control of heat exchange during the Fischer-Tropsch reaction processmay be advantageous for controlling selectivity towards the desiredproduct due to the fact that such added cooling may reduce or eliminatethe formation of undesired by-products from undesired parallel reactionswith higher activation energies.

The pressure within each individual heat exchange channel in themicrochannel reactor may be controlled using passive structures (e.g.,obstructions), orifices and/or mechanisms upstream of the heat exchangechannels or in the channels. By controlling the pressure within eachheat exchange channel, the temperature within each heat exchange channelcan be controlled. A higher inlet pressure for each heat exchangechannel may be used where the passive structures, orifices and/ormechanisms let down the pressure to the desired pressure. By controllingthe temperature within each heat exchange channel, the temperature inthe Fischer-Tropsch process microchannels can be controlled. Thus, forexample, each Fischer-Tropsch process microchannel may be operated at adesired temperature by employing a specific pressure in the heatexchange channel adjacent to or in thermal contact with the processmicrochannel. This provides the advantage of precisely controlledtemperatures for each Fischer-Tropsch process microchannel. The use ofprecisely controlled temperatures for each Fischer-Tropsch processmicrochannel provides the advantage of a tailored temperature profileand an overall reduction in the energy requirements for the process.

In a scaled up device, for certain applications, it may be required thatthe mass of the process fluid be distributed uniformly among themicrochannels. Such an application may be when the process fluid isrequired to be heated or cooled down with adjacent heat exchangechannels. The uniform mass flow distribution may be obtained by changingthe cross-sectional area from one parallel microchannel to anothermicrochannel. The uniformity of mass flow distribution may be defined byQuality Index Factor (Q-factor) as indicated below. A Q-factor of 0%means absolute uniform distribution.

$Q = {\frac{{\overset{.}{m}}_{\max} - {\overset{.}{m}}_{\min}}{{\overset{.}{m}}_{\max}} \times 100}$

A change in the cross-sectional area may result in a difference in shearstress on the wall. In one embodiment, the Q-factor for the microchannelreactor may be less than about 50%, or less than about 20%, or less thanabout 5%, or less than about 1%.

The superficial velocity for fluid flowing in the Fischer-Tropschprocess microchannels may be at least about 0.01 meters per second(m/s), or at least about 0.1 m/s, or in the range from about 0.01 toabout 100 m/s, or in the range from about 0.01 to about 10 m/s, or inthe range from about 0.1 to about 10 m/s, or in the range from about 1to about 100 m/s, or in the range from about 1 to about 10 m/s.

The free stream velocity for fluid flowing in the Fischer-Tropschprocess microchannels may be at least about 0.001 m/s, or at least about0.01 m/s, or in the range from about 0.001 to about 200 m/s, or in therange from about 0.01 to about 100 m/s, or in the range from about 0.01to about 200 m/s.

The conversion of CO from the fresh synthesis gas in the reactantmixture may be about 70% or higher, or about 75% or higher, or about 80%or higher, or about 90% or higher, or about 91% or higher, or about 92%or higher, or from about 88% to about 95%, or from about 90% to about94%, or from about 91% to about 93%. The one-pass conversion of CO forthe CO in the reactant mixture (i.e., fresh synthesis gas plus recycledtail gas) may be in the range from about 65% to about 90%, or from about70% to about 85%.

The selectivity to methane in the Fischer-Tropsch (FT) product may be inthe range from about 0.01 to about 10%, or about 1% to about 5%, orabout 1% to about 10%, or about 3% to about 9%, or about 4% to about 8%.

In one preferred process for conducting a Fischer-Tropsch reaction, areactant mixture in a microchannel reactor flows in contact with acatalyst to form a product comprising at least one higher molecularweight hydrocarbon product. Preferably, the catalyst is derived from acatalyst precursor comprising cobalt, optionally a promoter such as Pd,Pt, Rh, Ru, Re, Ir, Au, Ag and/or Os, and a surface modified support,wherein the surface of the support is modified by being treated withtitania, zirconia, magnesia, chromia, alumina, silica, or a mixture oftwo or more thereof. The product further comprises a tail gas, and atleast part of the tail gas can be separated from the higher molecularweight hydrocarbon product and combined with fresh synthesis gas to forma reactant mixture, the volumetric ratio of the fresh synthesis gas tothe tail gas in the reactant mixture being in the range from about 1:1to about 10:1, or from about 1:1 to about 8:1, or from about 1:1 toabout 6:1, or from about 1:1 to about 4:1, or from about 3:2 to about7:3, or about 2:1; the reactant mixture comprising H₂ and CO, the moleratio of H₂ to CO in the reactant mixture based on the concentration ofCO in the fresh synthesis gas being in the range from about 1.4:1 toabout 2:1 or from about 1.5:1 to about 2.1:1, or from about 1.6:1 toabout 2:1, or from about 1.7:1 to 1.9:1. Preferably, the conversion ofCO for the fresh synthesis gas in the reactant mixture is at least about70%, or at least about 75%, or at least about 80%, or at least about85%, or at least about 90%; and the selectivity to methane in theproduct is in the range from about 0.01 to 10%, or from about 1% toabout 10%, or from about 1% to about 5%, or from about 3% to about 9%,or from about 4% to about 8%.

The one-pass conversion of CO for the CO in the reactant mixture (i.e.,CO from the fresh synthesis gas plus CO from the tail gas can becombined with the fresh synthesis gas) may preferably be in the rangefrom about 70% to about 90%, or from about 70% to about 85%, or fromabout 70% to about 80%.

The CO conversion for the CO in fresh synthesis gas may be in the rangefrom about 88% to about 95%, or from about 90% to about 94%, or fromabout 91 to about 93%.

The FT product may comprise one or more hydrocarbons boiling at atemperature of at least about 30° C. at atmospheric pressure. The highermolecular weight aliphatic hydrocarbon product may comprise one or morehydrocarbons boiling above a temperature of about 175° C. at atmosphericpressure. The hydrocarbon product may comprise one or more paraffinsand/or one or more olefins of about 5 to about 100 carbon atoms. Theproduct may comprise one or more olefins, one or more normal paraffins,one or more isoparaffins, or a mixture of two or more thereof. Theproduct may be further processed using separation, fractionation,hydrocracking, hydroisomerizing, dewaxing, or a combination of two ormore thereof. The FT product may be further processed to form an oil oflubricating viscosity or a middle distillate fuel. The product may befurther processed to form a fuel.

The product may comprise a higher molecular weight hydrocarbon product,H₂O and H₂, the H₂O partial pressure for the product being in the rangefrom about 3 to about 10 bar, the H₂O/H₂ molar ratio for the productbeing in the range from about 1:1 to about 5:1, and the conversion of CObased on the total reactant mixture fed to the reactor (i.e., the sum offresh synthesis gas and recycle tail gas) being in the range from about70 to about 80%, or about 70 to about 85%, or from about 80 to about85%, or from about 82 to about 83%.

The Fischer-Tropsch product formed in the microchannel reactor maycomprise a gaseous product fraction and a liquid product fraction. Thegaseous product fraction may include hydrocarbons boiling below about350° C. at atmospheric pressure (e.g., tail gases through middledistillates). The liquid product fraction (the condensate fraction) mayinclude hydrocarbons boiling above about 350° C. (e.g., vacuum gas oilthrough heavy paraffins).

The Fischer-Tropsch product fraction boiling below about 350° C. may beseparated into a tail gas fraction and a condensate fraction, e.g.,normal paraffins of about 5 to about 20 carbon atoms and higher boilinghydrocarbons, using, for example, a high pressure and/or lowertemperature vapor-liquid separator, or low pressure separators or acombination of separators. The fraction boiling above about 350° C. (thecondensate fraction) may be separated into a wax fraction boiling in therange of about 350° C. to about 650° C. after removing one or morefractions boiling above about 650° C. The wax fraction may containlinear paraffins of about 20 to about 50 carbon atoms with relativelysmall amounts of higher boiling branched paraffins. The separation maybe effected using fractional distillation.

The Fischer-Tropsch product formed in the microchannel reactor mayinclude methane, wax and other heavy high molecular weight products. Theproduct may include olefins such as ethylene, normal and iso-paraffins,and combinations thereof. These may include hydrocarbons in thedistillate fuel ranges, including the jet or diesel fuel ranges.

Branching may be advantageous in a number of end-uses, particularly whenincreased octane values and/or decreased pour points are desired. Thedegree of isomerization may be greater than about 1 mole of isoparaffinper mole of n-paraffin, or about 3 moles of isoparaffin per mole ofn-paraffin. When used in a diesel fuel composition, the product maycomprise a hydrocarbon mixture having a cetane number of at least about60.

The Fischer-Tropsch product may be further processed to form alubricating base oil or diesel fuel. For example, the product made inthe microchannel reactor may be hydrocracked and then subjected todistillation and/or catalytic isomerization to provide a lubricatingbase oil, diesel fuel, aviation fuel, and the like. The Fischer-Tropschproduct may be hydroisomerized using the process disclosed in U.S. Pat.No. 6,103,099 or 6,180,575; hydrocracked and hydroisomerized using theprocess disclosed in U.S. Pat. No. 4,943,672 or 6,096,940; dewaxed usingthe process disclosed in U.S. Pat. No. 5,882,505; or hydroisomerized anddewaxed using the process disclosed in U.S. Pat. No. 6,013,171,6,080,301 or 6,165,949. These patents are incorporated herein byreference for their disclosures of processes for treatingFischer-Tropsch synthesized hydrocarbons and the resulting products madefrom such processes.

The hydrocracking reaction may be conducted in a hydrocrackingmicrochannel reactor and may involve a reaction between hydrogen and theFischer-Tropsch product flowing from the microchannel reactor, or one ormore hydrocarbons separated from the Fischer-Tropsch product (e.g., oneor more liquid or wax Fischer-Tropsch hydrocarbons). The Fischer-Tropschproduct may comprise one or more long chain hydrocarbons. In thehydrocracking process, a desired diesel fraction, for example, may beincreased by cracking a C₂₃₊ fraction to mid range carbon numbers of C₁₂to C₂₂. A wax fraction produced from the Fischer-Tropsch microchannelreactor may be fed to the hydrocracking microchannel reactor with excesshydrogen for a triple phase reaction. Under reaction conditions atelevated temperatures and pressures, a fraction of the liquid feed mayconvert to a gas phase, while the remaining liquid fraction may flowalong the catalyst. In conventional hydrocracking systems, a liquidstream forms. The use of a microchannel reactor for the hydrocrackingreaction enables unique advantages on a number of fronts. These mayinclude kinetics, pressure drop, heat transfer, and mass transfer.

The Fischer-Tropsch hydrocarbon products that may be hydrocracked in thehydrocracking microchannel reactor may comprise any hydrocarbon that maybe hydrocracked. These may include hydrocarbons that contain one or moreC—C bonds capable of being broken in a hydrocracking process. Thehydrocarbons that may be hydrocracked may include saturated aliphaticcompounds (e.g., alkanes), unsaturated aliphatic compounds (e.g.,alkenes, alkynes), hydrocarbyl (e.g., alkyl) substituted aromaticcompounds, hydrocarbylene (e.g., alkylene) substituted aromaticcompounds, and the like.

The feed composition for the hydrocracking microchannel reactor mayinclude one or more diluent materials. Examples of such diluents mayinclude non-reactive hydrocarbon diluents, and the like. The diluentconcentration may be in the range from zero to about 99% by weight basedon the weight of the Fischer-Tropsch product, or from zero to about 75%by weight, or from zero to about 50% by weight. The diluents may be usedto reduce the viscosity of viscous liquid reactants. The viscosity ofthe feed composition in the hydrocracking microchannel reactor may be inthe range from about 0.001 to about 1 centipoise, or from about 0.01 toabout 1 centipoise, or from about 0.1 to about 1 centipoise.

The ratio of hydrogen to Fischer-Tropsch product in the feed compositionentering the hydrocracking microchannel reactor may be in the range fromabout 10 to about 2000 standard cubic centimeters (sccm) of hydrogen percubic centimeter (ccm) of Fischer-Tropsch product, or from about 100 toabout 1800 sccm/ccm, or from about 350 to about 1200 sccm/ccm. Thehydrogen feed may further comprise water, methane, carbon dioxide,carbon monoxide and/or nitrogen.

The H₂ in the hydrogen feed may be derived from another process such asa steam reforming process (product stream with H₂/CO mole ratio of about3), a partial oxidation process (product stream with H₂/CO mole rationof about 2), an autothermal reforming process (product stream with H₂/COmole ratio of about 2.5), a CO₂ reforming process (product stream withH₂/CO mole ratio of about 1), a coal gassification process (productstream with H₂/CO mole ratio of about 1), and combinations thereof. Witheach of these feed streams the H₂ may be separated from the remainingingredients using conventional techniques such as membranes oradsorption.

The hydrocracked Fischer-Tropsch product may comprise a middledistillate fraction boiling in the range of about 260-700° F. (127-371°C.). The term “middle distillate” is intended to include the diesel, jetfuel and kerosene boiling range fractions. The terms “kerosene” and “jetfuel” boiling range are intended to refer to a temperature range of260-550° F. (127-288° C.) and “diesel” boiling range is intended torefer to hydrocarbon boiling points between about 260 to about 700° F.(127-371° C.). The hydrocracked Fischer-Tropsch product may comprise agasoline or naphtha fraction. These may be considered to be the C₅ to400° F. (204° C.) endpoint fractions.

A schematic view of an FT test reactor system is shown in FIG. 1. Asshown in the FIGURE, CO, H₂, and N₂ can be metered through masscontrollers 2 and the gases are reacted in microchannel reactor 4 andthe products pass into a separator or separators. The productcomposition can be analyzed by gas chromatography such as the microGCshown in FIG. 1.

FIG. 1 shows three points for condensing products. There is no limit tothe number of condensing stages that could be used, including just twostages or even a single stage for separating an aqueous stage or acombined aqueous solution from multiple condensers. In the context ofthe present invention, a first condensed aqueous stream is typicallycondensed at a higher temperature than a second aqueous stream. Withreference to the FIG. 1, a first aqueous stream could be collected fromthe condenser at T1 and a second aqueous stream could be collected fromthe condenser at T2. Alternatively, it is possible that the aqueousfractions from T1 and T2 could be combined into a first aqueous streamwhile the fraction collected from a condenser at T3 could be sent to awater treatment facility. It should be understood that the separate usesfor differing aqueous fractions is not required in every embodiment ofthe invention, since, in some embodiments, any or all of the aqueousfractions could be used for fracking.

In some preferred embodiments, all water is collected in a singleseparator and the full flow is subjected to stripping, prior tosubsequent use and/or biological treatment.

In the case of a relatively hot (T1) and cold (T2) separation, theliquid separated at the higher temperature will contain less carbon thanthe cold separator. As a result, it may be necessary to strip only thecold separator water. The hot separator water and stripped coldseparator water could then used and/or sent to biological treatment.

1-10. (canceled)
 11. A water composition, comprising: at least 90%water, less than 20 mg/L, or 10 mg/L, of each of the following:formaldehyde, propionaldehyde, butyraldehyde, diethyl ketone; at least10 mg/L of each of the following: formic acid, acetic acid, propionicacid, n-butryic acid, and n-valeric acid; at least 50 mg/L methanolwherein the mass ratio of methanol to the sum of(propanol+butanol+pentanol+hexanol+heptanol+octanol+nonanol) is greaterthan 1, or greater than 2 or greater than 5 or greater than 10 orgreater than
 50. 12. The water composition of claim 11, possessing oneor any combination of the following characteristics: 10 ppm or lessaromatics; pH between 3.0 and 3.5; 40 mg/L, 20 mg/L, 10 mg/L, 5 mg/L orless acetone; 50 to 8000 mg/L methanol; up to about 3500, or up to about1000, or up to about 500 mg/L ethanol; mass ratio of formic acid tomethanol at least 0.030, 0.08; mass ratio of propionic acid to propanolat least 0.030, 0.06, 1.0; 14C/13C ratio is at least 90% lower thanpresent in biological carbon; 0.1 to 1.0% C; less than 1.0 mg/L of eachof the following: formaldehyde, propionaldehyde, butyraldehyde, diethylketone; less than 0.1 mg/L of each of the following: formaldehyde,propionaldehyde, butyraldehyde, diethyl ketone. 13-19. (canceled)
 20. Amethod of fracking, comprising: creating water in a Fischer-Tropsch (FT)process to form created water; storing the created water in a locationclose to a fracking site; injecting the created water in a well at thefracking site; wherein a product stream from the FT process is separatedinto a first aqueous stream and a second aqueous stream; and whereinwater from the first aqueous stream is stored and injected into the wellat the fracking site.
 21. The method of claim 20 further comprisingsubjecting the first aqueous stream to a stripping operation where a gasis passed through the first aqueous stream.
 22. The method of claim 20wherein at least a portion of the second aqueous stream is reacted in asteam reforming reaction or an autothermal reforming reaction.